Process of oxidizing oils



June 1932- M. CHAPPELL ET AL 1,865,081

PROCESS OF OXIDIZING OILS Filed NOV. 26, 1929 C 004 ER TI/VK INVENTORSMfl/PV/M L. C/IFPPELL BY TG/VM OOM/LE'A/ ATTORNEY Patented June 28, 1932UNITED s ATEs PATENT OFFICE MARVIN L. GHALPPELL, or WATSON, AND TOMH.DOWLE1\T, on Los ANGELES, CALIFOR- NIA, ASSIGNORS TO RIGHFIELD OILCOMPANY or CALIFORNIA, on Los ANGELES, CALIFORNIA, .A CORPORATION onDELAWARE PROGESS F OXIDIZING OILS Application filed November 26, 1929.Serial No. 409,937.

This invention relates to a process of oxidizing liquids with anaeriform fluid, such as air, oxygen or oxygen bearing gases, either withor without the aid of a catalyst, in which 5 the oxidizing reaction isexothermic.

More. specifically this invention relates to oxidizing oils or oilproducts such as petroleum oils, petroleum oil residuum, shale oils,

animal or vegetable oils, wherein the oxida-' 0 tlon actlon 1sexothermic and a uniform oxidizing temperature is beneficial ornecessary for obtaining the desired product or products, or results inan economical saving of time; such for example as in the oxidation 5 ofrape-seed oil or cotton-seed oil, to increase the viscosity, theoxidation or partial oxidation of linseed oil or other like oils eitherwith or Without the aid of a catalyst; or in the manufacture of oxidizedasphaltic products suitable as a cementing agent for roofing material,battery sealing compounds and for like purposes where an asphalticcementing agent is required with a relatively high melting point whichwill be sufliciently ductile and flexible.

In the conventional method of oxidizing oils, or petroleum oil residuum,air or air and steam is introduced into the container holding the oil orresiduum, through spray 9 pipes and at the same time the oil is heatedto a temperature suflicient to obtain the desired oxidizing reaction.difficult to obtain a uniform product, since a uniform temperaturecannot be readily maintained due to the exothermic heat of the oxidizingreaction. The added exothermic heat frequently overheats the oil orasphaltic" residuum to a cracking temperature or produces otherundesired decomposition reactions. In oxidizing asphaltic residuum withair, overheating produces a product which is more brittle and lessductile than if a regulated uniform oxidizing temperature had beenmaintained.

Also by the well-known batch still method, the time required to converta batch of asphaltic residuum intoan oxidized product suitable forbattery sealing compounds, or for the manufacture of roofing felt,requires approximately 24 hours, while by our inven- By such methods itis tion the reaction is accomplished in about one half the time.

Now, we have discovered an improvement in the art of oxidizing oils andpetroleum oil residuum in which the difiiculties and variousdisadvantages before mentioned may be overcome by the use of air, cooledto a temperature sufficient to extract the exothermic heat of theoxidizing reaction, thereby maintaining a substantially uniformtemperature at the required degree, this temperature depending upon theoil to be oxidized, the extent of oxidationand the product desired. Forexample, in oxidizing petroleum asphaltic residuum the temperature mayran e from approximately 400 to 550 degrees in oxidizing rape-seed oilor cotton-seed oil a temperature ranging from approximately 180 to 300degrees F. may be employed and in oxidizing linseed oil in the presenceof a catalyst such as a manganese salt or compound, a temperature ofapproximately 180 to 300 degrees F. is employed.

We are aware that coollng ackets through which a cooling liquid flows,surrounding or partly surrounding the container, in which an oxidationaction is effected, is well-known in the art for partly extracting theexother- ..mic heat produced from the oxidation of oils.

However, such methods are not entirely satisfactory, since the productbeing oxidized may solidify and coat the inside of the container, thusinsulating the inside surface of the container to such an extent thatthe transmission of heat to the cooling medium is too slow to take awaythe excess exothermic heat produced, whereby the oil, or residuum may beoverheated and undesired decomposition reactions take place.

Briefly stated, our invention comprises continuously commingling anoxidizable oil or an asphaltic residuum at the required oxidizingtemperature, with an aeriform fluid containing oxygen, such as air,cooled to such a temperature that the exothermic heat produced by theoxidizing reaction will be continuously and immediately extracted fromthe body of the oil or residuum, by the cooler residual aeriform fluidleaving the body of oil or residuum.

The use of a cooled aeriform fluid containing oxygen for producingoxidized asphalt, or oxidized oils to increase the viscosity thereof,may be employed by our invention in any batch or continuous system.

An object of the invention is to provide a simple, efficient andeconomical process or method by which oils, asphaltic residuum or otheroxidizable liquids may be converted into desired oxidized products at aminimum production cost and with a minimum consumption of time.

Another object of the invention is to provide an efficient andeconomical process by which'asphaltic residuum may be converted b anycontinuous or batch system, into oxidized asphaltic products, which willhave relatively high melting points, flash and at the same time will besufiiciently ductile and flexible.

Another object of the invention is to provide a simple and efiicientprocess for oxidizing oilsor manufacturing oxidized asphaltic products,in which the various characteristics,

of fluidity or ductility, melting point, flash, etc., required by thedifferent branches of the individual art, may be controlled, separatelyor in combination with other products, such for example as mixingoxidized asphalt made by this invention with natural asphalt or asphaltmade by steam distillation.

With the foregoing preliminary explanation the preferred embodiment ofour invention will now be more fully explained by reference to theaccompanying drawing and for the purpose of simplifying the description,reference will be made to petroleum oil resid uum only.

In the drawing, pipe 4, controlled by valve 5, connects oxidizingcontainer 3 near the top to a source of supply of petroleum oil residu-vum not shown. ontainer 3 is stationed in the top of furnace 1. Furnace 1is provided with burner 2 which leads to a source of fuel supply notshown. Pipe 14, controlled by valve 15, is connected to container 3' atthe top and leads to a source of steam supply not shown. Pipe 16connects steam pipe 14 to branch pipes 18. Branch pipes 18, controlledby valves 17, connect pipe 16 to pipes 25. Pipe 20, connects air pipe 19to branch pipes 25. Air pipe 19 leads to a source of com- I pressed airnot shown. Pipe 23, connects cooled air pipe 22 to branch pipes 26.Cooled air pipe 22 leads to a source of cooled compressed air not shown.Branch pipes 26, controlled by valves 24, connect pipe 23 to pipes 25.Pipes 25, controlled by valves 21,. extend through the top of container3 ending in spray pipes 9. Container 3 is provided I with bafiie plates8 which divide the containor or oxidizing chamber 3 into a plurality ofconnected compartments. Pipe 6, controlled by valve 7 leads to a storagetank not shown. Pipes 11 connect the compartments of con- 27 to the topof distillate tank 30. Pipe 32,

controlled by valve 33 leads to a storage not shown. A residual airoutlet pipe 31 is con nected to the top of distillate tank 30.

The preferred operation of the apparatus just described is as followsThe oil to be oxidized, such as a petroleum oil residuum, is chargedinto oxidizing container 3 to any desired level by opening valve 5 inthe pipe 4, the pipe 4 leading to a source of supply not shown. Thecontainer 3 is provided with a plurality of connected compartmentsseparated by baflie plates 8, each baffle plate having an opening at thebottom, although this opening may be at any place in the baffleplatebelow the oil level, so that in the continuous operation of theapparatus the oil under oxidation will flow through the compartments andout through discharge line 6, the rate of flow being governed by therate of oxidation and controlled by regulated openings of valves 5 and 7in the pipes 4 and 6 to maintain a substantially constant level. Whencontainer 3 has been filled to the desired level valve 5 is tentativelyclosed and the residuum in container 3 is heated to the requiredoxidizing temperature by' burner 2 in the furnace 1, this temperatureranging from approximately 400 to 550 degrees F. for petroleum oilresiduum and usually somewhat lower for animal or vegetable oils, thedegree of heat depending upon the oil to be oxidized and the productdesired. At the beginning of the heating operation of the residuum inoxidizing container 3, as well as during the oxidation operation, asmall amount of steamis preferably continuously introduced into the topI of each compartment of oxidizing container 3, from steam pipe 14 by aregulated opening of valve 15, to prevent explosive or burning mixturesfrom forming in the top of container 3. In the drawing only one pipeconnection is shown for introducing steam into the top of thecompartments of container 3 and it is to be understood that steam pipe14 has branch pipe connections (not shown) to the other compartments.

It is desirable during this preliminary heating operation to introduceregulated quantities of air into each compartment of the oxidizingcontainer 3, the rate of flow ments of container 3 is carried out byregulated openings of valves 21in the branch pipes 25, branch pipes 25being connected to pipe 20. Pipe 20 is connected to air pipe 19, whichleads to a'source of air not shown.

The air passing through pipes 25 and out through the spray pipes 9 intothe compartments of oxidizing container 3 is usually equallyproportioned, although equally proportioned amounts of air are notabsolutely essential for each compartment, and 'in certain cases moreair may be introduced into the last compartment or compartments toobtain the required oxidation.

If desired, steam may be introduced into the compartments of container 3along with the air during the preliminary heating operation to free theresiduum of volatile hydrocarbons and water, or steam may be introducedat intervals or continuously during the oxidation operation. Theintroduction of steam into the residuum is carried out by regulatedopenings of valves 17 in the branch pipes 18. The branch pipes 18 areconnected to pipe 16. Pipe 16 is connected to steam pipe 14.

When the petroleum oil residuum has attained a temperature at which itis desired to carry out the oxidizing operation, such for example as 480degrees F., burner 2 in the furnace 1 is shut off to such an extent thatthere will be substantially no further transmission of heat to container3, and at the same time cooled air preferably approximate- 1y at 10 F.from pipe 22 is introduced into each compartment of container 3 alongwith the aircoming through pipe 19, the cooled air, which may be atanydesire'dtemperature lower than atmospheric F. to 0 F. or lower),being in quantities suflioient to extract the excess exothermic heatproduced by the oxidizing reaction.

The cooled air, or cooled aeriform fluid containing oxygen, employed inthe oxidizing operation, may be obtained by any refrigeration or coolingmethod, such for example as passing air through a brine solution cooledto 10 F. by an ammonia or sulphur dioxide refrigerating system or by anyof the Wellknown multiple compression, cooling and expansion systems forcooling or hquetymg a1r.

The introduction of cooled air into the compartments of container 3along with the air coming through pipe 19, is carried out by regulatedopenings of valves 24 in the branch pipes 26. Branch pipes 26 areconnected to pipe 23 and pipe 23 is connected to cooled air rnainsubstantially constant. Valve 5 is now opened to Sucha'degree as toadmit a regulated flow of the petroleumoil residuum to be oxidized, therate of flow being governed by ual air outlet pipe 31.

gaseous products of the oxidizing reaction pass out of the variouscompartments of oxidizing container 3 through pipes 11 into pipe 12 andthen through cooler coil 27, stationed in the cooler box 28, whereby thecondensable hydrocarbons and steam are liquefied and pass from coolercoil 27, together with the residual air and gaseous products, throughpipe 29 into distillate tank 30. In distillate tank 30 the residual airand gaseous products separate from the condensed liquid products andpass out of the system through the resid- From distillate tank 30, thecondensed oil and water may be conducted to a storage not shown throughthe pipe 32 controlled by valve 30.

The operation of our invention in batch lots, is carried outsubstantially the same as in the continuous system just described withthe exception that the petroleum oil residuum is not permitted to flowthrough the compart ments of container 3, during the oxidizingoperation, valves 5 and; 7 remaining closed. Also the use of cool air isusually discontinued during the latter part of the oxidizing operationand heat applied by burner 2 to maintain the required constant elevatedoxidizing temperature for completing the oxidizing reaction. Theapplication of heat to container 3 and the discontinued use of cooledair is usually necessary when the petroleum oil residuum has beenoxidized to such a degree air may be employed to finish the oxidationoperation, introduced through the pipe 19 and branch pipes 25 which endin spray pipes 9.

The operation of this invention may be carried out undersuper-atmospheric pressure or under pressure less than atmospheric, de-

pending upon the oil to be oxidized and the product desired. Forexample,in the manufacture of high melting point oxidized asphalt from apetroleum oil or petroleum oil residuum containing a high percentage ofrelatively low boiling hydrocarbons, the oxidizing operation asheretofore described, may be conducted under vacuum ranging from 755 to5 mm. of mercury or less, absolute pressure, and in the production ofoxidized asphaltic products from low" Baum gravity petroleum residuum,which Contains substantially no relatively low boiling hydrocarbons, theoxidizing operations may be conducted at atmospheric pressure or athigher pressure.

While the process herein described is well adapted for carryingout theobjects of the present invention, it is to be understood that variousmodifications and changes may be made without departing from the spiritof the invention, such for example as the employment of a plurality ofconnected oxidizing containers, and the invention includes all suchchanges and modifications as come within the scope of the appendedclaims.

What We claim is:

1. A process of oxidizing asphaltic oils, comprising, maintaining asupply of asphaltic oil in a container provided with a plurality ofdistinct but connected compartments through which the asphaltic oilcontinually passes, at an oxidizing temperature, continuouslyintroducing and commingling regulated streams of cooled air with the oilin each compartment of the container, continuously Withdrawing theresidual air and volatile oil products from each compartment of thecontainer, continuously introducing a regulated:

. stream of asphaltic oil into the first compartment of the container,continuously extractingthe heat of the oxidizing reaction by regulatingthe temperature of the cooled introduced air, and discharging theoxidized oil from the system.

2. A process of oxidizing asphaltic oils, comprising, maintaining asupply of asphaltic oil in a container with a plurality of distinct butconnected compartments through which the asphaltic oil continuouslypasses at an elevated oxidizing temperature, continuously introducing aregulated stream of as phaltic oil into the first compartment of thecontainer, continuously introducing an individual supply of cooled airinto each compartment of the container at a temperature sufficient toextract the exothermic heat of the oxidizing reaction, continuouslywithdrawing the residual air and volatile oil products from eachcompartment of the container, and discharging the oxidized product fromthe system.

3. A process of oxidizing asphaltic oils, comprising, maintaining asupply of asphaltic oil in a container provided with a plurality ofdistinct but connected compartments through which the asphaltic oilcontinuously passes at temperatures of approximately 400 to 550 degreesF., continuously introducing a regulated stream of asphaltic oil intothe first compartment of the container, continuously introducing andcommingling regulated streams of cooled air with the asphaltic oil ineach compartment of the container at a temperature and in quantitiessufficient to extract the exothermic heat of the oxidizing reaction,continuously withdrawing the residual air and volatile oil products fromeach compartment of the container, and

discharging oxidized asphaltic oil from the system.

4. A process of oxidizing asphaltic oils, comprising, maintaining asupply of asphaltic oil in a'container providedwith a plurality ofdistinct but connected compartments through which the asphaltic oilcontinuously passes, at an elevated oxidizing temperature, continuouslyintroducin a regulated stream of asphaltic oil into the rst compartmentof the container, continuously introducing regulated streams of air,cooled to a temperature sufiicient to extract the exothermic heat of theoxidizing reaction, into the supply of asphaltic oil in eachcompartment, continuously withdrawing the residual air and volatile oilproducts from each compartment of the container and finally dischargingthe oxidized oil from the system.

5. A process of oxidizing asphaltic oils, comprising, maintaining asupply of asphaltic oil in a container provided with a plurality ofdistinct but connected compartments through which the asphaltic oilcontinuously passes, maintaining the supply of asphaltic oil at atemperature of approximately 480 degrees F., continuously introducing aregulated stream of asphaltic oil into the first compartment of thecontainer, continuously introducing and commingling regulated streams ofcooled air with the asphaltic oil in each compartment of the container,continuously Withdrawin the residual air and volatileoil products romeach compartment of the container, and discharging the oxidizedasphaltic oil from the system.

6. Aprocess of producing oxidized asphalt, comprising, continuouslyintroducing and passing petroleum oil residuum through a series ofdistinct but connected compartments in a container holding a bulk supplyof petroleum oil residuum, maintaining the bulk supply of petroleum oilresiduum at an elevated oxidizing temperature, introducing separatelyregulated streams of cooled air into each compartment of the container,continuously separating and withdrawing the residual air and volatileoil products from the residuum undergoing oxidation, continuouslyextracting from the residuum undergoing oxidation the excess heatproduced by the oxidation reaction by regulating the temperature of thecooled air, maintaining the temperature of the residuum and the time ofpassage through the connected compartments so that the residuum will beoxidized to the required degree and then passing the oxidized residuumout of the system.

7. A process of forming oxidized asphalt, comprising continuouslyintroducing and passing petroleum oil residuum in a regulated streamflow through a series of distinct but connected compartments in acontainer holding a bulk supply of petroleum oil residuum, maintaining toil residuum at a temperature of approximately 400 to 550 degrees F.,introducing and commingling separately regulated streams of air, cooledto a temperature of approximate- 1y 10 degrees F., with the petroleumoil residuum in each compartment of the container, continuouslyseparating and withdrawing the residual air and volatile products fromthe residuum undergoing oxidation in each compartment of said container,continuously extracting from the residuum the excess heat produced bythe oxidation reaction by regulating the quantity of introduced cooledair, maintaining the temperature of the residuum and time of passagethrough the connected compartments so that the residuum will be oxidizedto the required degree and continuously passing the oxidized residuumout of the system.

In testlmony whereof we aflix our signatures.

MARVIN L. CHAPPELL. TOM H. DOWLEN.

e bulk supply of. petroleum

